CN1004992B - Rare-earth catalyzer using alloy cellular carrier and its preparation - Google Patents

Rare-earth catalyzer using alloy cellular carrier and its preparation Download PDF

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CN1004992B
CN1004992B CN86105768.6A CN86105768A CN1004992B CN 1004992 B CN1004992 B CN 1004992B CN 86105768 A CN86105768 A CN 86105768A CN 1004992 B CN1004992 B CN 1004992B
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carrier
catalyst
present
temperature
alloy
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CN86105768A (en
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徐锦航
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Beijing University of Technology
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Beijing University of Technology
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Priority to CN86105768.6A priority Critical patent/CN1004992B/en
Priority to EP87110139A priority patent/EP0255625B1/en
Priority to DE3789638T priority patent/DE3789638D1/en
Priority to US07/078,468 priority patent/US4820678A/en
Publication of CN86105768A publication Critical patent/CN86105768A/en
Publication of CN1004992B publication Critical patent/CN1004992B/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
    • B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
    • Y10S502/524—Spinel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
    • Y10S502/525—Perovskite

Abstract

The present invention relates to a rare earth catalyst of an alloy honeycomb carrier, which is used for industrial waste gas purification, automobile exhaust and air purification. The present invention is characterized in that the carrier is a thin wall honeycomb body which is made of porous aluminum-alloy tape which has high electric resistance, good thermoduric ability and metal rags on both faces of the tape. Catalyzing active materials of the carrier is the non-noble-metal composition oxide of ABO3 or K2MgF4 crystal types and has the main components of light mixed rare-earth and iron. The present invention has an attaching method that various metallic elements are rapidly coated strictly according to stoichiometry proportion, and the method is a drying method. The present invention has the advantages of high intensity, good thermal conductivity, great processing ability, low price, lead prevention, etc.

Description

The method for preparing rare earth metal composite oxide/alloy cellular body catalyst
The rare earth catalyst of alloy cellular carrier is used for industrial waste gas purifying, automobile exhaust gas purifying and air cleaning.It is converted into carbon dioxide and water by oxidation or reduction reaction with harmful waste gas, emits reaction heat simultaneously, and its reaction equation is as follows:
Domestic and international existing alloy cellular carrier catalyst all is to make catalytic active substance with noble metal, is base material with general aluminium carbon steel or the stainless steel strip of containing; Existing rare earth catalyst then or make DNAcarrier free or with particles such as alundum (Als or is made carrier with ceramic honeycomb, and that its catalytic active substance is used is ABO 3Crystal formation or K 2MgF 4Composite oxide of metal such as crystal formation, its Main Ingredients and Appearance are variable valency metals such as lanthanide series metal, alkaline-earth metal and cobalt, nickel, copper, manganese.The present invention is formed by complex rare-earth oxidate containing valuable metal and the two strong bonded of alloy cellular carrier, is a kind of novel combination catalyst.
One, carrier
Carrier of the present invention is general high temperature resistant, high-resistance siderochrome aluminium or nickel chromium triangle aluminum strip, with
Cat. represent catalyst
T. represent temperature
Other alloy cellular carrier differences are, to be rolled into that 0.07～0.08mm is thick to it, 50mm(or 25mm or 30mm) wide long band, again in the two-sided aperture (pitch-row 1.1～1.2mm) that shuts out 0.4 * 0.4mm, all there is the protrusion of metallic bur power on limit, two-sided hole, wherein most belt will shut out ripple (wave height 1.1～1.7mm is about pitch of waves 3mm) through corrugating machine again.These bands also need pass through the treatment process of giving of oil removing, acid etching alligatoring and thermal activation (heating 1～2 hour) in 650 ℃～750 ℃ oxidizing atmospheres, could obtain the surface has γ-AL 2O 3The activation base material of protective layer.And then a corrugated ribbon and a flat rubber belting together around volume, can obtain garden shape or oval honeycomb substrate.If ripple bar and riglet be spaced also can obtain rectangle, honeycomb substrate such as square, can decide as required.Accompanying drawing 1 is a carrier work flow schematic diagram.
Carrier of the present invention is compared with granular or ceramic honeycomb carrier, and following characteristics are arranged:
1, because the intensity of alloy is big, thermal conductivity good, so the performance of shatter-proof, shock-resistant, corrosion-resistant, the anti-temperature fluctuation significantly of this carrier all is better than ceramic honeycomb carrier significantly.
2, because the ductility of alloy is good, so the honeycomb hole hole wall of this carrier is very thin, cell densities and free cross-sectional area are just big, thereby the disposal ability of this catalyst unit volume is done being twice of carrier than ceramic honeycomb.
3, because alloy surface has formed one deck with γ-AL 2O 3Be main oxidation film, make carrier have good high temperature oxidation resistance, good corrosion resistance, the while has been improved the specific area of carrier again.Again because aluminium is moved to the surface from metal inside, so the phenomenon that surface film oxide comes off can not take place.
Carrier of the present invention is compared with domestic and international existing alloy cellular carrier, because the aperture of double-sided belt burr has increased the adhesive force and the specific area of carrier surface, make the catalytic activity thing be easy to coat, and catalytic activity is good.Especially can manage to form metallic bond between alloy cellular carrier surface and the catalytic active substance, it is attached very firm that coating of the present invention is carried.This helps prolonging the service life of catalyst very much.
In addition, the directly energising heating of high temperature resistant, high-resistance carrier, so make heating element with catalytic performance after energising with the catalyst that the inventive method is made, its surface can promptly reach enough temperature and carry out to guarantee catalytic reaction, thereby can save waste gas and give hot device, save the capital expenditure and the running expense of arrangement for catalytic purification.
Two, catalytic active substance:
Catalytic active substance of the present invention belongs to perovskite structure (ABO 3Crystal formation) or spinel structure (K 2MgF 4Crystal formation), but compare, be characterized in that Main Ingredients and Appearance is light mishmetal and iron with general rare earth catalyst, advantage be raw material sources extensively and price is more honest and cleaner.In above-mentioned two kinds of structures, the A position is chemical atomic number 11-51, the base metal cation of 56-71 or 89-103, and the B position is ionic radius 0.4～1.4A ° a variable valency metal cation.At ABO 3A position population of ions should equal the population of ions of B position in the structure; At A 2BO 4In the structure, the population of ions of A position should be twice in the population of ions of B position.The electric charge sum of cation A and B is equal to the electric charge sum of oxonium ion.The invention is characterized in, at ABO 3In the type structure, the A position is 0.6～0.8 with light mishmetal or its gram atom ratio of lanthanum, strontium or calcium, and its gram atom ratio is 0.4～0.2, B position iron, the gram atom ratio is 0.5～0.8, manganese and/or copper are or/and nickel, the gram atom ratio is 0.5～0.2, also can add trace palladium, and the gram atom ratio is 0.01.At K 2MgF 4In the crystalline structure (with A 2BO 4Expression), the A position is with light mishmetal and lanthanum, and the gram atom ratio is 1.4～1.8, strontium and calcium, and the gram atom ratio is 0.6～0.2, B position iron, the gram atom ratio is 0.5～0.8, nickel, the gram atom ratio is 0.5～0.2.
Among the present invention, the representative formula of catalytic active substance is:
(RE 1-xSr x) (Fe 1-yMn y) O 3Or
〔La 1-xSr x〕〔Fe （1-y-ε）Mn yPd ε *〕O 3
Or
Figure 86105768_IMG3
Gram atom is than X=0.2～0.4 y=0.2～0.5 ε=0.01 in the formula
X 1＝0.1～0.3，X 2＝0.1～0.3，y 1＝0.2～0.5
*: when needing to reduce reacting initial temperature, just in dividing, the B hyte adds the palladium of denier.
Because catalytic active substance of the present invention is multiple composite oxide of metal, and is more loose; Rolling again on the carrier substrate has a lot of uniform small pores, so this catalyst is similar to sound-absorbing porous material.After the sound wave incident, cause the vibration of air in the material void, and produce friction, make acoustic energy change heat energy into, make noise attentuation with hole wall.When several catalyst were placed at interval by certain distance, air communication spread suddenly after crossing honeycomb hole, enters the honeycomb through hole once more, once more diffusion.This is just meeting micropore and is enlarging noise-cancelling theory, makes the alloy honeycomb catalyst group play inhibitory action to pneumatic noise, makes catalytic reactor can become silencer simultaneously.
Three, carry attached method
Year attached method of catalyst is meant that catalytic active substance is attached to the method on the carrier.Usually adopt infusion process, promptly carrier is immersed in the solution of catalytic active substance, dry again after dipping a period of time, roasting forms.Other also have coprecipitation, electroless plating method, and spray drying process, galvanoplastic etc., also useful freeze-drying, mixing method, metallurgical concretion method, ion blast technique etc. are made catalyst.All can not required various metallic element strictnesses be attached on the metallic carrier than ground surely by stoichiometry with said method.As infusion process, the alloy carrier is immersed in the plating bath of multiple metal ion, ion-exchange reactions can take place, the electrode potential difference of various metallic elements, the ability of then carrying out ion-exchange reactions is also different, so original proportioning is destroyed, being attached on the carrier is the metallic element of those electronics that are easy to get most mostly.If use hot spray process, then since the proportioning of the molten point of each metallic element, boiling point difference, coating also can't definitely grasp.
The present invention then be a kind of can be multi-component catalytic active substance strictly by stoichiometric ratio, equably, fixed than the method that is attached on the alloy cellular carrier securely, can be named quick coating seasoning.Its technological process is as shown in Figure 2: the activated carrier bar is around rolling up in around axle (1) and (2) (for example axle (1) is around ripple bar, and axle (2) is around riglet); Roll out simultaneously, divide upper and lower two layers to enter quick painted groove (3); The dryer section (4) that the belt of band masking liquid enters the coating kiln is immediately decomposed section (5) and preliminary oxidation panel (6) by salt again, is around in around axle (7) and (8) again.Corrugated ribbon and flat rubber belting can be together around, also can be separately around.On demand after the moulding,, give hot arc 15, oxidation panel 16 and cooling section 17 by the oxidation kiln along track 14 with forming blocks 12 dolly 13 of packing into.Release body of heater, catalyst just preparation finishes.1～2 meter/minute of band walking speed, 0.5～0.6 second coating time.The temperature of coating kiln dryer section is controlled at 110～200 ℃, decomposes 350～450 ℃ of sections, and it was 350～450 ℃ that 650～750 ℃ of oxidation panels, oxidation kiln give hot arc, by 0.5 hour; 650～850 ℃ of oxidation panels were by 1.5 hours; Cooling section was by 0.5 hour.If once be coated with irregularly or not enough amount, can be coated with for the second time.The waste gas that the coating kiln is discharged can be extracted out emptying after purifier purifies by blower fan 9.The characteristics of this method are: masking liquid is strict with required stoichiometry preparation, mix; Coating is at room temperature carried out, and speed is very fast, makes the metal ion in metallic carrier and the masking liquid have little time to take place displacement reaction.This has just guaranteed the chemical constitution of coating and the performance of catalyst.
Embodiment:
(1) carrier processing
Buy the thick siderochrome aluminium OCr of 1.0mm 21Al 6Band, its Main Ingredients and Appearance are Cr21-24%, Al6.5-7.5%; Other contain rare earth 0.03%, Ti0.15%, CO0.5%, C≤0.06%, Si≤0.06%, Mn≤0.06%, S≤0.03%, P≤0.03%; Fe is a surplus.1200 ℃ of maximum operation (service) temperatures.Percentage elongation 〉=12%, 90 ° of number of times 〉=5 of clod wash time.Than resistance 1.4 ± 0.1 Ω mm 2/ M.
Through two rollers (1) and four rollers (2) cold-rolling mill for several times, (800 ± 20 ℃ of annealing temperatures) to roll into 0.07-0.08mm thick.Again through rolling a machine (3), at the two-sided uniform small pores that shuts out the band burr, aperture 0.4 * 0.4mm, pitch-row 1.2mm, hole penetrance 〉=90%.Shut out ripple through corrugating machine (4) again, pitch of waves 3.1mm, wave height can be regulated, at 1.1-1.7mm.
The siderochrome aluminium strip is through 50 ℃ of degreaser oil removings (7).The washing (8) after again through 38% technical hydrochloric acid etch (9) 5-8 minute.In ultrasonic cleaner (12), thoroughly clean with deionized water (13).Activated again stove (14) passes through in 650 ℃ to 750 ℃ oxidizing atmospheres, makes the surface form the oxide film protection layer of q.s.
(2) Preparation of Catalyst
1, claims lanthanum nitrate 234.84 grams, strontium nitrate 63.49 grams, ferric nitrate 318.98 grams, manganese nitrate 35.79 grams, palladium nitrate 2.30 grams, be dissolved in water, evenly mix, make 2000 milliliters of solution, put into the painted groove 3 of quick apparatus for coating (Fig. 2).The dryer section temperature that be coated with kiln this moment is decomposed the section temperature between 350-450 ℃ between 110-200 ℃, the temperature of preliminary oxidation panel is between 700-750 ℃.Starting drive then, passed through oil removing, the siderochrome aluminium corrugated ribbon of processing such as alligatoring and activation and flat rubber belting be respectively from rolling out simultaneously around axle 1 with around axle 2, divide up and down two layers with 1-2 rice/minute speed pass through device, on axle 6, corrugated ribbon and flat rubber belting are together around being rolled into the honeycomb type Cylinder.Can get (La 0.7Sr 0.3) (Fe 0.79Mn 0.2Pd 0.01) O 34～5 kilograms of catalyst.Catalyst block after a large amount of moulding 500 * 300 * 150mm that can pack into 3Dolly 13, pushed away a car every 10 minutes and advance that oxidation is close carries out final oxidation.This kiln gives 350～450 ℃ of hot arc temperature, and dolly was giving hot arc totally 30 minutes.700～750 ℃ of this kiln oxidation panel temperature, dolly was oxidation panel totally 90 minutes.At last, dolly passed through cooling section with 30 minutes, was pushed outside the kiln discharge.In the gained catalyst, 7～8% of gross weight is a catalytic active substance.
The applicability of this catalyst and clean-up effect are asked for an interview Fig. 3,4,5.It sees Fig. 6,7,8 for details with the performance comparison (carrier is identical) of precious metals palladium catalyst.It is shown in Fig. 9 to the clean-up effect of air steel cylinder air.Its air speed characteristic and acoustic absorptivity are shown in table 1,2.
The contrast of table 1 air speed characteristic
Figure 86105768_IMG4
*Waste gas contains C 3H 61% contains CO0.2%
Table 2 catalyst acoustic absorptivity
Figure 86105768_IMG5
This catalyst is used for the enamelling machine tail gas clean-up, and physical life is above 4 years
2, claim light mishmetal 98.0 grams, add 100 milliliters in nitric acid, dissolving claims strontium nitrate 84.65 grams, ferric nitrate 238.7 grams, and manganese nitrate 35.79 grams, copper nitrate 37.51 grams, all water-soluble.Evenly mix with the lanthanum nitrate hexahydrate that makes, get 2000 milliliters of solution, put into quick apparatus for coating.Can make (RE with the same method 0.6Sr 0.4) (Fe 0.59Mn 0.2Cu 0.2) O 3About 4 kilograms of catalyst.
This catalyst is used for the purification and the noise elimination, respond well of automobile exhaust, and actual life is above 5.8 ten thousand kilometers.The car exhaust gas purifier of this catalyst (HF type clarifier) and the correction data of former car silencer are shown in table 3 and table 4.
3, claim lanthanum nitrate 454.90 grams, strontium nitrate 63.49 grams, calcium nitrate 49.22 grams, ferric nitrate 242.27 grams, nickel nitrate 73.08 grams are dissolved in water, are mixed with 2500 milliliters of mixed solutions, put into the painted groove of quick apparatus for coating.Except the temperature that is coated with kiln and oxidation kiln changes into 800～850 ℃, all the other methods and condition are all with example 1.Gained catalyst (La 1.4Sr 0.3Ca 0.3) (Fe 0.6Ni 0.4) O 4About 5 kilograms.
When this catalyst is used for the waste gas pollution control and treatment of nitrogen-containing oxide, during waste gas air speed 10000 -1, during 300 ℃ of temperature, the purifying rate 99.4% of 100ppmNOx.
The catalyst that makes with above (routine 1-example 3) method can be shaped flexibly according to user's requirement.Can make 250 * 200 * 50mm as the catalyst that purified industrial waste gas is used 3Rectangle or 200 * 200 * 50mm 3Square block be assembled into the catalyst frame, the heating element with catalytic performance that also can make φ 280mm * 50mm or the φ 200mm * 30mm catalytic reaction tube of industrial waste gas arrangement for catalytic purification of packing into.When being used in automobile exhaust gas purifying and eliminating the noise, can make garden band pieces such as φ 100mm * 25mm or φ 140mm * 25mm, also can make (φ 340+170 * 170) mm 2* 25 or (φ 120+47 * 47) mm 2The ellipse garden shape piece of * 25mm.
Table 3 BJ-492 engine rig test result *
*HF type clarifier dress ABO 31.7 liters of type catalyst, engine uses doped fuel
Table 4 uses the comparing result of HF type automobile fuel saving purifying muffler (representing with second) and former commercially available silencer (representing with first)
Figure 86105768_IMG7
General characteristic by institute of the present invention controlling catalyst is schematically illustrated in table 5
Table 5 general characteristic
Figure 86105768_IMG8
Can regenerate behind this catalyst failure.Regeneration test the results are shown in table 6.Result of the test proves that the catalytic activity that the invertibity factor causes descends, and can regenerate at reason.Entirely ineffective catalyst can reuse its carrier, behind the recoat active constituent, comes into operation once more.
Table 6 catalyst regeneration result of the test
Figure 86105768_IMG9
Description of drawings
Fig. 1 carrier work flow schematic diagram
6 water-baths 11 of 1 duo mill, rinsing bowl
2, four-high mill 7, degreaser 12, ultrasonic cleaner
3, roll a machine 8, rinsing bowl 13, tank
4, rolling corrugated machine 9, acid etching groove 14, activation furnace
5, around axle 10, rotating shaft
Fig. 2, Preparation of Catalyst schematic flow sheet
15, around axle 22, forming room
16, quick painted groove 23, preformed catalyst piece
17, coating kiln dryer section 24, dolly
18, 〃 〃 〃 decomposes section 25, mill train
19, 〃 〃 〃 oxidation panel 26, oxidation kiln give hot arc
20, air exhauster 27, 〃 〃 〃 oxidation panel
21, NOx clarifier 28, 〃 〃 〃 cooling section
Fig. 3, Fig. 4, Fig. 5, ABO 3The type alloy honeycomb catalyst is to the purification curve air inlet air speed 10000h of organic exhaust gas -1, (ppm) is as follows for organic matter title and concentration:
(1), n-hexane 9065ppm (2), isooctane 8565ppm
(3), cyclic ethylene 5279ppm (4), glacial acetic acid 5232ppm
(5), formaldehyde 5000ppm (6), cyclohexanone 6855ppm
(7), ethanol 5475ppm (8), n-butanol 10000ppm
(9), ethyl acetate 4870ppm (10), benzene 10000ppm
(11), cresols 5807ppm (12), pyridine 600ppm
(13), acetonitrile 6011ppm (14), carbonoxide 9200ppm
Fig. 6, catalytic activity comparison diagram
A, ABO of the present invention 3Type catalyst B, 0.5% palladium catalyst
Waste gas contains propylene 10000ppm, waste gas air speed 10000h -1
Fig. 7, heat endurance comparison diagram
A, ABO of the present invention 3Catalyst B, 0.5% palladium catalyst
Heat endurance refers to that catalyst changes through the propylene purifying rate (η) of two hours front and back of 800 ℃ of gas shocks.Waste gas contains propylene 10000ppm, air 10000h -1
Δ η Heat is steady=η Behind the high temperature impact-η Before the high temperature impact
Fig. 8, anti-lead comparison diagram
A, ABO of the present invention 3The type catalyst
B, 0.5% palladium catalyst
Anti-lead refers to that catalyst is by before and after the lead poisoning, to the variation of propylene purifying rate (η).Waste gas contains propylene 10000ppm, waste gas air speed 10000h -1
△ η Anti-plumbous=η After the lead poisoning-η Before the lead poisoning
The purification curve of THC (THC) in Fig. 9, the steel cylinder air
The steel cylinder air contains THC 57ppm, air air speed 3500h -1

Claims (7)

1, a kind of preparation contains the ABO of rare earth 3The method of type composite oxides/alloy cellular body catalyst is characterized in that it is made up of the following step:
(1), two-sided rolling had aperture, high temperature resistant, the high-resistance siderochrome aluminium or the nichrome aluminum alloy band of hole sideband burr shape protrusion carry out oil removing, acid etching alligatoring, and activate 1～2 hour in 650 ℃～750 ℃ oxidizing atmosphere;
(2), make above-mentioned alloy band at normal temperatures by 1～2 meter/minute speed between 0.5～0.6 second fast by salting liquid by the catalytic activity thing of stoichiometric number preparation;
(3), under 110 ℃～200 ℃ temperature, press the speed rapid draing above-mentioned alloy band that be loaded with catalytic activity thing identical with (2);
(4), carrying out salt under 350 ℃～450 ℃ temperature decomposes;
(5), under 650 ℃～850 ℃ temperature, carry out oxidation processes;
(6), the cooling back is around volume (or arrangement) moulding.
CN86105768.6A 1986-07-30 1986-07-30 Rare-earth catalyzer using alloy cellular carrier and its preparation Expired CN1004992B (en)

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Application Number Priority Date Filing Date Title
CN86105768.6A CN1004992B (en) 1986-07-30 1986-07-30 Rare-earth catalyzer using alloy cellular carrier and its preparation
EP87110139A EP0255625B1 (en) 1986-07-30 1987-07-14 A method for preparing rare earth metal catalysts with honeycomb-like alloy as supports.
DE3789638T DE3789638D1 (en) 1986-07-30 1987-07-14 Manufacturing method for rare earth metal catalysts with honeycomb-shaped carrier materials from metal reinforcements.
US07/078,468 US4820678A (en) 1986-07-30 1987-07-27 Method for preparing rare earth metal catalysts with honeycomb-like alloy supports and catalysts obtained thereby

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CN86105768.6A CN1004992B (en) 1986-07-30 1986-07-30 Rare-earth catalyzer using alloy cellular carrier and its preparation

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CN1004992B true CN1004992B (en) 1989-08-16

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DE3741887A1 (en) * 1987-12-10 1989-06-22 Asea Brown Boveri CATALYST AND METHOD FOR THE PRODUCTION THEREOF
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EP0255625B1 (en) 1994-04-20
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DE3789638D1 (en) 1994-05-26
US4820678A (en) 1989-04-11
CN86105768A (en) 1987-11-11

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